Poly(ester-carbonate)s, articles formed therefrom, and methods of manufacture

ABSTRACT

A poly(carbonate-ester) copolymer including carbonate units of the formula (I); and ester units of the formula (II) wherein: T is a C 2-20  alkylene, a C 6-20  cycloalkylene, or a C 6-20  arylene; and R 1  and J are each independently a bisphenol A divalent group, or a phthalimidine divalent group or a third divalent group of the formula (III), (IV), (V), (VI) or (VII) wherein X a  is a C 6-12  polycyclic aryl, C 3-18  mono- or polycycloalkylene, C 3-18  mono- or polycycloalkylidene, -(Q 1 )x-G-(Q 2 ) y - group wherein Q 1  and Q 2  are each independently a C 1-3  alkylene, G is a C 3-10  cycloalkylene, x is 0 or 1, and y is 1, provided that the at least one bisphenol A divalent group, at least one phthalimidine divalent group, and at least one third divalent group are present in the poly(carbonate-ester) copolymer.

BACKGROUND

This disclosure is directed to poly(ester-carbonate)s, thermoplasticcompositions containing the poly(ester-carbonate)s, articles formedtherefrom, and their methods of manufacture.

Polycarbonates are useful in the manufacture of articles and componentsfor a wide range of applications, from automotive parts to electronicappliances. Because of their broad use, particularly in automotive,lighting and consumer electronics industries, it is desirable to providepolycarbonates having high heat capacities and good surface propertiessuch as the ability to be metalized. In addition, many of theseapplications require thin wall thicknesses or high flow lengths.Accordingly it is also desirable for these compositions to have goodmelt flow lengths (low melt viscosities) and good melt stability (lackof melt viscosity shift) at the processing conditions.

SUMMARY

A poly(ester-carbonate) comprises carbonate units of the formula

andester units of the formula

wherein:

-   -   T is a C₂₋₂₀ alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀        arylene; and    -   R¹ and J are each independently a bisphenol A divalent group of        the formula

-   -   or a phthalimidine divalent group of the formula

wherein

-   -   R^(a) and R^(b) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂        alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy,    -   each R³ is independently a C₁₋₆ alkyl,    -   R⁴ is hydrogen, C₁₋₆ alkyl or phenyl optionally substituted with        1 to 5 C₁₋₆ alkyl groups,    -   p, q, and j are each independently 0 to 4,

or a third divalent group of the formula

wherein R^(c) and R^(d) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy,

each R⁶ is independently C₁₋₃ alkyl or phenyl,

X^(a) is a C₆₋₁₂ polycyclic aryl, C₃₋₁₈ mono- or polycycloalkylene,C₃₋₁₈ mono- or polycycloalkylidene, -(Q¹)_(x)-G-(Q²)_(y)- group whereinQ¹ and Q² are each independently a C₁₋₃ alkylene, G is a C₃₋₁₀cycloalkylene, x is 0 or 1, and y is 1, and m and n are eachindependently 0 to 4,

provided that the at least one bisphenol A divalent group, at least onephthalimidine divalent group, and at least one third divalent group arepresent in the poly(carbonate-ester) copolymer.

In another embodiment, disclosed is a thermoplastic compositioncomprising the poly(ester-carbonate).

In yet another embodiment, an article comprises the above-describedpoly(ester-carbonate) or thermoplastic composition.

In still another embodiment, a method of manufacture of an articlecomprises molding, extruding, or shaping the above-describedpoly(ester-carbonate) or thermoplastic composition into an article.

The above described and other features are exemplified by the followingdrawings, detailed description, examples, and claims.

DETAILED DESCRIPTION

The inventors hereof have found that poly(ester-carbonate)s disclosedherein can have high heat resistance and good surface properties. Thepoly(ester-carbonate)s, also known as polyester-polycarbonates, comprisecarbonate units of the formula (1)

andester units of the formula (2)

wherein T is a divalent group derived from a dicarboxylic acid(including a reactive derivative thereof), and can be, for example, aC₂₋₂₀ alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀ arylene, preferablyC₆₋₂₀ divalent aromatic radical such as a divalent isophthaloyl radical,a divalent terephthaloyl radical, or a combination thereof, and R¹ and Jare each independently a bisphenol A divalent group or a phthalimidinedivalent group, or a third divalent group different from the bisphenol Adivalent group and the phthalimidine divalent group, provided that atleast one bisphenol A divalent group, at least one phthalimidinedivalent group, and at least one third divalent group are present in thepoly(carbonate-ester) copolymers.

Aromatic dicarboxylic acids that can be used to prepare the polyesterunits include isophthalic or terephthalic acid,1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether,4,4′-bisbenzoic acid, or a combination comprising at least one of theforegoing acids. Acids containing fused rings can also be present, suchas in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specificdicarboxylic acids include terephthalic acid, isophthalic acid,naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, or acombination comprising at least one of the foregoing acids. A specificdicarboxylic acid comprises a combination of isophthalic acid andterephthalic acid wherein the weight ratio of isophthalic acid toterephthalic acid is 91:9 to 2:98.

Aliphatic dicarboxylic acid that can be used to prepare the polyesterunits include a linear C₆₋₂₀ aliphatic dicarboxylic acid (which includesa reactive derivative thereof), preferably a linear C₆-C₁₂ aliphaticdicarboxylic acid (which includes a reactive derivative thereof).Specific dicarboxylic acids include n-hexanedioic acid (adipic acid),n-decanedioic acid (sebacic acid), and alpha, omega-C₁₂ dicarboxylicacids such as dodecanedioic acid (DDDA).

The bisphenol A divalent group is of the formula

The phthalimidine divalent group is of the formula

wherein R^(a) and R^(b) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy, preferably a C₁₋₃ alkyl, eachR³ is independently a C₁₋₆ alkyl, R⁴ is hydrogen, C₁₋₆ or C₂₋₆ alkyl orphenyl optionally substituted with 1 to 5 C₁₋₆ alkyl groups, and p, q,and j are each independently 0 to 4, preferably 0 to 1. For example, thephthalimidine carbonate units can be of formula (3a)

wherein R⁵ is hydrogen, phenyl optionally substituted with up to fiveC₁₋₆ alkyl groups, or C₁₋₄ alkyl, preferably C₂₋₄ alkyl. In anembodiment, R⁵ is hydrogen or phenyl. When R⁵ is phenyl, R¹ and J can bederived from 2-phenyl-3,3′-bis(4-hydroxy phenyl)phthalimidine (alsoknown as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one or N-phenylphenolphthalein or “PPPBP”).

The third divalent group is of the formula (4), (5), (6), (16), or (17)

wherein R^(c) and R^(d) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy, each R⁶ is independently C₁₋₃alkyl or phenyl, preferably methyl, X^(a) is a C₆₋₁₂ polycyclic aryl,C₃₋₁₈ mono- or polycycloalkylene, C₃₋₁₈ mono- or polycycloalkylidene,-(Q¹)_(x)-G-(Q²)_(y)- group wherein Q¹ and Q² are each independently aC₁₋₃ alkylene, G is a C₃₋₁₀ cycloalkylene, x is 0 or 1, and y is 1; andm and n are each independently 0 to 4.

Exemplary third divalent group includes the following:

wherein R^(c) and R^(d) are the same as defined herein for formulas(4)-(6), (16), and (17), each R¹ is independently hydrogen or C₁₋₄alkyl, m and n are each independently 0 to 4, each R² is independentlyC₁₋₄ alkyl or hydrogen, and g is 0 to 10. In a specific embodiment thethird divalent group is derived from1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane,1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, or a combination thereof.Preferably, the third divalent group is derived from1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (BPA TMC).

R¹ and J divalent groups can be derived from the correspondingbisphenols. The bisphenol A divalent group is derived from bisphenol A

The phthalimidine divalent group is derived from a phthalimidinebisphenol of the formula

wherein R³, R⁴, R^(a), R^(b), p, q, and j are the same as defined hereinfor formula (3).

The third divalent group is derived from a bisphenol of the followformula

wherein R^(c), R^(d), R⁶, m, and n are the same as defined herein forformulas (4)-(6), (16), and (17).

The molar ratio of ester units to carbonate units in the copolymers canvary broadly, for example 1:99 to 99:1, preferably 10:90 to 90:10, morepreferably 25:75 to 75:25, or 2:98 to 15:85 or 2:1 to 1:2, depending onthe desired properties of the final composition.

The poly(ester-carbonate)s comprise 45 mol % to 70 mol % of thebisphenol A divalent groups, 2 mol % to 50 mol % of the phthalimidinedivalent groups, and 5 mol % to 30 mol % of the third divalent groups,each based on the sum of moles of the bisphenol A divalent groups,phthalimidine divalent groups, and third divalent groups. In specificembodiments, the poly(ester-carbonate)s comprise 50 mol % to 65 mol % ofthe bisphenol A divalent groups, 4 mol % to 20 mol % of thephthalimidine divalent groups, and 3 mol % to 28 mol % of the thirddivalent groups, each based on the sum of the moles of the bisphenol Adivalent groups, phthalimidine divalent groups, and third divalentgroups.

The poly(ester-carbonate)s can have a weight average molecular weight of10,000 to 50,000 Daltons, preferably 18,000 to 25,000 Daltons, asmeasured by gel permeation chromatography (GPC), using a crosslinkedstyrene-divinylbenzene column and calibrated to bisphenol Ahomopolycarbonate reference standards. GPC samples are prepared at aconcentration of 1 mg per ml, and are eluted at a flow rate of 1.5 mlper minute.

In an embodiment, the poly(ester-carbonate)s have flow properties usefulfor the manufacture of thin articles. Melt volume flow rate (oftenabbreviated MVR) measures the rate of extrusion of a thermoplasticthrough an orifice at a prescribed temperature and load.poly(ester-carbonate)s useful for the formation of thin articles canhave an MVR of 2 to 50, preferably 5 to 40 cm³/10 minutes, measured at337° C. under a load of 6.7 kg in accordance with ASTM D1238-04.

The poly(ester-carbonate)s have a high glass transition temperature(Tg). The Tg of the poly(ester-carbonate)s is 195 to 235° C., preferably200 to 230° C., determined by differential scanning calorimetry (DSC) asper ASTM D3418 with a 20° C./min heating rate.

The poly(ester-carbonate)s can have high heat resistance. The heatdeflection temperature (HDT) of the poly(ester-carbonate)s is 180 to215° C., preferably 200 to 210° C., measured flat on a 80×10×4 mm barwith a 64 mm span at 0.45 MPa according to ISO 75/Bf.

The poly(ester-carbonate)s can have high Vicat softening temperature. Inan embodiment, the poly(ester-carbonate)s have a Vicat B 120 of 195 to235° C., preferably 200 to 230° C., measured according to ISO 306.

The poly(ester-carbonate)s can have excellent metallization properties.In an embodiment, a metalized sample of the poly(ester-carbonate)s has adefect onset temperature that is within 20 degrees Celsius of the heatdeflection temperature of the copolycarbonate where the HDT is measuredflat on a 80×10×4 mm bar with a 64 mm span at 0.45 MPa according to ISO75/Bf. In another embodiment, a metalized sample of thepoly(ester-carbonate)s has a defect onset temperature that is within 10degrees Celsius of the heat deflection temperature of thecopolycarbonate where the HDT is measured flat on a 80×10×4 mm bar witha 64 mm span at 0.45 MPa according to ISO 75/Bf. In another embodiment,the metalized sample has a defect onset temperature of 200 to 220° C.

The poly(ester-carbonate)s can have a visual transmission (Tvis) of 70%to 90% measured on HAZE-GUARD plus from BYK-Gardner instruments.

The poly(ester-carbonate)s can further have a Notched Izod Impact of 5to 10 KJ/m², determined in accordance with ISO 180 under a load of 5.5 Jat 23° C. on a sample plaque of 3 mm thickness.

Polycarbonates can be manufactured by processes such as interfacialpolymerization and melt polymerization, which are known, and aredescribed, for example, in WO 2013/175448 A1 and WO 2014/072923 A1. Anend-capping agent (also referred to as a chain stopper agent or chainterminating agent) can be included during polymerization to provide endgroups, for example monocyclic phenols such as phenol, p-cyanophenol,and C₁-C₂₂alkyl-substituted phenols such as p-cumyl-phenol, resorcinolmonobenzoate, and p- and tertiary-butyl phenol, monoethers of diphenols,such as p-methoxyphenol, monoesters of diphenols such as resorcinolmonobenzoate, functionalized chlorides of aliphatic monocarboxylic acidssuch as acryloyl chloride and methacryoyl chloride, andmono-chloroformates such as phenyl chloroformate, alkyl-substitutedphenyl chloroformates, p-cumyl phenyl chloroformate, and toluenechloroformate. Combinations of different end groups can be used.Branched polycarbonate blocks can be prepared by adding a branchingagent during polymerization, for example trimellitic acid, trimelliticanhydride, trimellitic trichloride, tris-p-hydroxyphenylethane,isatin-bis-phenol, tris-phenol TC(1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA(4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethylbenzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, andbenzophenone tetracarboxylic acid. The branching agents can be added ata level of 0.05 to 2.0 wt. %. Combinations comprising linearpolycarbonates and branched polycarbonates can be used.

Also disclosed are thermoplastic compositions comprising thepoly(ester-carbonate)s. In addition to the poly(ester-carbonate)s, thethermoplastic compositions can further comprise a polycarbonatehomopolymer such as a bisphenol A homopolycarbonate, an additionalpoly(ester-carbonate), or a combination comprising at least one of theforegoing. The poly(ester-carbonate)s can be present in an amount of 40wt. % to 90 wt. % and the polycarbonate homopolymer, the additionalpoly(ester-carbonate), or a combination thereof can be present in anamount of 30 wt. % to 60 wt. %, each based on the total weight of thethermoplastic composition.

The additional poly(ester-carbonate)s can further contain, in additionto recurring carbonate chain units derived from a dihydroxy compound,repeating ester units of formula (7)

wherein J₂ is a divalent group derived from a dihydroxy compound (whichincludes a reactive derivative thereof), and can be, for example, aC₂₋₁₀ alkylene, a C₆₋₂₀ cycloalkylene a C₆₋₂₀ arylene, or apolyoxyalkylene group in which the alkylene groups contain 2 to 6 carbonatoms, preferably, 2, 3, or 4 carbon atoms; and T₂ is a divalent groupderived from a dicarboxylic acid (which includes a reactive derivativethereof), and can be, for example, a C₂₋₂₀ alkylene, a C₆₋₂₀cycloalkylene, or a C₆₋₂₀ arylene. Copolyesters containing a combinationof different T or J groups can be used. The polyester units can bebranched or linear.

Specific dihydroxy compounds include resorcinol, bisphenols used to makethe carbonate units of formula (1), a C₁₋₈ aliphatic diol such as ethanediol, n-propane diol, i-propane diol, 1,4-butane diol, 1,6-cyclohexanediol, 1,6-hydroxymethylcyclohexane, or a combination comprising at leastone of the foregoing dihydroxy compounds.

Aromatic dicarboxylic acids that can be used to prepare the polyesterunits include isophthalic or terephthalic acid,1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether,4,4′-bisbenzoic acid, or a combination comprising at least one of theforegoing acids. Acids containing fused rings can also be present, suchas in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Aliphaticdicarboxylic acids that can be used include C₆₋₂₀ aliphatic dicarboxylicacids (which includes the terminal carboxyl groups), preferably linearC₈₋₁₂ aliphatic dicarboxylic acid such as decanedioic acid (sebacicacid); and alpha, omega-C₁₂ dicarboxylic acids such as dodecanedioicacid (DDDA). Specific dicarboxylic acids that can be used includeterephthalic acid, isophthalic acid, naphthalene dicarboxylic acid,1,6-cyclohexane dicarboxylic acid, or a combination comprising at leastone of the foregoing acids. A combination of isophthalic acid andterephthalic acid wherein the weight ratio of isophthalic acid toterephthalic acid is 91:9 to 2:98 can be used.

Specific ester units include ethylene terephthalate units, n-propyleneterephthalate units, n-butylene terephthalate units, ester units derivedfrom isophthalic acid, terephthalic acid, and resorcinol (ITR esterunits), and ester units derived from sebacic acid and bisphenol A. Themolar ratio of ester units to carbonate units in thepoly(ester-carbonate)s can vary broadly, for example 1:99 to 99:1,preferably, 10:90 to 90:10, more preferably, 25:75 to 75:25, or from2:98 to 15:85. In some embodiments the molar ratio of ester units tocarbonate units in the poly(ester-carbonate)s can vary from 1:99 to30:70, preferably 2:98 to 25:75, more preferably 3:97 to 20:80, or from5:95 to 15:85.

The thermoplastic compositions can include various additives ordinarilyincorporated into polymer compositions of this type, with the provisothat the additive(s) are selected so as to not significantly adverselyaffect the desired properties of the thermoplastic composition, inparticular melt flow, thermal, and surface properties. Such additivescan be mixed at a suitable time during the mixing of the components forforming the composition. Additives include fillers, reinforcing agents,antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV)light stabilizers, plasticizers, lubricants, mold release agents,antistatic agents, colorants such as such as titanium dioxide, carbonblack, and organic dyes, surface effect additives, radiationstabilizers, flame retardants, and anti-drip agents. A combination ofadditives can be used, for example a combination of a heat stabilizer,mold release agent, and ultraviolet light stabilizer. In general, theadditives are used in the amounts generally known to be effective. Forexample, the total amount of the additives (other than any impactmodifier, filler, or reinforcing agents) can be 0.01 to 5 wt. %, basedon the total weight of the thermoplastic composition. The thermoplasticcompositions can be manufactured by various methods known in the art.For example, powdered polycarbonate, and other optional components arefirst blended, optionally with any fillers, in a high speed mixer or byhand mixing. The blend is then fed into the throat of a twin-screwextruder via a hopper. Alternatively, at least one of the components canbe incorporated into the composition by feeding it directly into theextruder at the throat or downstream through a sidestuffer, or by beingcompounded into a masterbatch with a desired polymer and fed into theextruder. The extruder is generally operated at a temperature higherthan that necessary to cause the composition to flow. The extrudate canbe immediately quenched in a water bath and pelletized. The pellets soprepared can be one-fourth inch long or less as desired. Such pelletscan be used for subsequent molding, shaping, or forming.

The thermoplastic composition can have an MVR of 2 to 50, preferably 5to 35 cm³/10 minutes, measured at 337° C. under a load of 6.7 kg inaccordance with ASTM D1238-04.

The thermoplastic compositions are generally processed at conditionsthat give suitable melt flow without significant degradation or shift inthe melt viscosity. In an embodiment, the thermal plastic compositionscan have at a given temperature a melt viscosity of less than 1000 Pa·sat 644.5 sec⁻¹ (according to ISO11443) and have a shift in meltviscosity of less than 30% at that temperature over 30 min under anitrogen atmosphere as measured in a dynamic oscillatory time sweeprheology at a fixed angular frequency of 10 radians/sec.

In another embodiment, the thermal plastic compositions can have at agiven temperature a melt viscosity of less than 900 Pa·s at 644.5 sec⁻¹and have a shift in melt viscosity of less than 25% at that temperatureover 30 min under a nitrogen atmosphere as measured in a small amplitudeoscillatory time sweep rheology at a fixed angular frequency of 10radians/sec.

The thermoplastic composition can have a heat deflection temperature(HDT) of 180 to 215° C., measured flat on a 80×10×4 mm bar with a 64 mmspan at 0.45 MPa according to ISO 75/Bf.

The thermoplastic composition can have excellent metallizationproperties. In an embodiment, a metalized sample of the thermoplasticcomposition has a defect onset temperature that is within 10 degreesCelsius of the heat deflection temperature of the copolycarbonate wherethe HDT is measured flat on a 80×10×4 mm bar with a 64 mm span at 0.45MPa according to ISO 75/Bf.

Shaped, formed, or molded articles comprising the poly(ester-carbonate)sor the thermoplastic compositions are also provided. Thepoly(ester-carbonate)s and compositions can be molded into useful shapedarticles by a variety of methods, such as injection molding, extrusion,rotational molding, blow molding, and thermoforming. Some example ofarticles include computer and business machine housings such as housingsfor monitors, handheld electronic device housings such as housings forcell phones, electrical connectors, and components of lighting fixtures,ornaments, home appliances, roofs, greenhouses, sun rooms, swimming poolenclosures, and the like. Additional exemplary articles include a plug,a plug housing, a switch, an electrical conductor, a connector, anelectric board, a lamp holder, a lamp cover, a lamp bezel, a reflector,a signal indicator, glazing, a lens, a lens holder, a waveguide element,a collimator, a light emitting diode, a diffuser sheet, a safety pane, afilm, a film laminate, a safety goggle, and a visor.

The article comprising the poly(ester-carbonate)s or the thermoplasticcompositions can be a metallized article. The metallized articlecomprises, for example, a substrate comprising thepoly(ester-carbonate)s, or thermoplastic compositions, with a metallayer disposed on the at least one side of the substrate.

The substrate can be for example, a film. The substrate can be made bymolding the poly(ester-carbonate)s or the thermoplastic compositions.The molding methods are not particularly limited, and various knownmolding methods can be listed, for example, injection molding, gasassist injection molding, vacuum molding, extrusion, compressionmolding, calendaring, rotary molding, etc. Of these, molding is usuallycarried out by injection molding.

The metal layer can be disposed onto the surface of the substrate withthe aid of electrocoating deposition, physical vapor deposition, orchemical vapor deposition or a suitable combination of these methods.Sputtering processes can also be used. The metal layer resulting fromthe metallizing process (e.g., by vapor deposition) can be 0.001 to 50micrometers (am) thick.

A base coat can be present between the substrate and the metal layer.However, it is advantageous to form the metal layer directly on thesubstrate surface without forming an undercoat. The surfaces of thesubstrate are smooth and good gloss can be obtained even by direct metalvapor deposition without treating the substrate with a primer. Moreover,the release properties of the molded substrate during injection moldingare good. Accordingly, the surface properties of the molded substrateare superior without replication of mold unevenness.

Chrome, nickel, aluminum, etc. can be listed as examples of vaporizingmetals. Aluminum vapor deposition is used in one embodiment as metalvapor deposition. The surface of the molded substrate can be treatedwith plasma, cleaned, or degreased before vapor deposition in order toincrease adhesion.

The metallized article can have a protective layer disposed on the metallayer. “Protective layer” refers for example, to a layer which is madeof a binder or a high molecular weight polymer and formed on theoutermost (e.g., the UV blocking) layer, so as to exert the effects ofpreventing marring and improving mechanical properties of the multilayerarticle. The protective layer can be clear or pigmented and beformulated, for example, with nitrocellulose or synthetic polymersconfigured to quickly dry by evaporation without chemical reaction withthe layer on which they are disposed, providing a solid protectivelayer. The protective coating material can further be thinned withalcohols. In certain applications, the thickness of the protective layeris minimized. The thickness of the protective layer can be, for example,0.2 am or less.

The metallized articles can have little mold shrinkage, have goodsurface gloss even when metal layers are directly vapor deposited, andthe vapor deposited surfaces do not become cloudy or have rainbowpatterns even on heating of the vapor deposited surface. In particular,the metallized article can have no surface defects visible to the eye.

Illustratively, the metallized article has a metallized surface, whereinthe surface can exhibit a gloss of greater than 95 units, or greaterthan 1700 units, measured at 20 degrees using a trigloss meter. Themetallized surface can also retain 85%, 88%, 90%, 95% or more of itsgloss after heat aging at 150° C. for 1 hour, measured at 20 degreesusing a micro trigloss meter. A base coat (undercoat) can be presentbetween the article and the metallized surface, or a surface of thearticle can be directly metallized.

Metallized articles have applications in optical reflectors and can beused for automotive headlamps, headlight extensions, and headlampreflectors, for indoor illumination, for vehicle interior illuminationand for the like.

Set forth below are various embodiments of the disclosure.

Embodiment 1

A poly(carbonate-ester) copolymer comprising

carbonate units of the formula

and

ester units of the formula

wherein:

-   -   T is a C₂₋₂₀ alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀        arylene; and    -   R¹ and J are each independently a bisphenol A divalent group of        the formula

or a phthalimidine divalent group of the formula

wherein

-   -   R^(a) and R^(b) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂        alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy,    -   each R³ is independently a C₁₋₆ alkyl,    -   R⁴ is hydrogen, C₁₋₆ alkyl or phenyl optionally substituted with        1 to 5 C₁₋₆ alkyl groups,    -   p, q, and j are each independently 0 to 4,        or a third divalent group of the formula

wherein R^(c) and R^(d) are each independently a C₂₋₁₂ alkyl, C₁₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy,

each R⁶ is independently C₁₋₃ alkyl or phenyl,

X^(a) is a C₆₋₁₂ polycyclic aryl, C₃₋₁₈ mono- or polycycloalkylene,C₃₋₁₈ mono- or polycycloalkylidene, -(Q¹)_(x)-G-(Q²)_(y)- group whereinQ¹ and Q² are each independently a C₁₋₃ alkylene, G is a C₃₋₁₀cycloalkylene, x is 0 or 1, and y is 1, and

m and n are each independently 0 to 4,

provided that the at least one bisphenol A divalent group, at least onephthalimidine divalent group, and at least one third divalent group arepresent in the poly(carbonate-ester) copolymer.

Embodiment 2

The poly(carbonate-ester) copolymer of Embodiment 1, wherein T is aC₆₋₂₀ divalent aromatic radical.

Embodiment 3

The poly(carbonate-ester) copolymer of Embodiment 1 or Embodiment 2,wherein T is a divalent isophthaloyl radical, a divalent terephthaloylradical, or a combination thereof.

Embodiment 4

The poly(carbonate-ester) copolymer of any one of Embodiments 1 to 3,wherein the molar ratio of the carbonate units relative to the esterunits is 2:1 to 1:2.

Embodiment 5

The poly(carbonate-ester) copolymer of any one of Embodiments 1 to 4,wherein p, q, and j are zero, and R⁴ is hydrogen, methyl, or phenyl.

Embodiment 6

The poly(carbonate-ester) copolymer of any one of Embodiments 1 to 5,wherein the third divalent group has the structural formula

wherein

each R¹ is independently hydrogen or C₁₋₄ alkyl,

each R² is independently C₁₋₄ alkyl or hydrogen, and

g is 0 to 10.

Embodiment 7

The poly(carbonate-ester) copolymer of Embodiment 6, wherein R¹ ismethyl or hydrogen, R² is methyl or ethyl, and g is 0 to 3.

Embodiment 8

The poly(carbonate-ester) copolymer of any one or more of Embodiments 1to 7, wherein the third divalent group is derived from1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane.

Embodiment 9

The poly(carbonate-ester) copolymer of any one or more of Embodiments 1to 5, wherein the third divalent group has the structural formula

wherein R^(c) and R^(d) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy; and m and n are eachindependently 0 to 4.

Embodiment 10

The poly(carbonate-ester) copolymer of any one or more of Embodiments 1to 9, wherein the phthalimidine divalent group is present in an amountof 5 mol % to 30 mol % based on the sum of the moles of the bisphenol Adivalent group, the phthalimidine divalent group, and the third divalentgroup.

Embodiment 11

The poly(carbonate-ester) copolymer of any one or more of Embodiments 1to 10, wherein third divalent group is present in an amount of 2 mol %to 50 mol % based on the sum of the moles of the bisphenol A divalentgroup, the phthalimidine divalent group, and the third divalent group.

Embodiment 12

The poly(carbonate-ester) copolymer of any one or more of Embodiments 1to 11, wherein the bisphenol A divalent group is present in an amount of45 mol % to 70 mol % based on the sum of the moles of the bisphenol Adivalent group, the phthalimidine divalent, and the third divalentgroup.

Embodiment 13

A thermoplastic composition comprising a poly(carbonate-ester) copolymerof any one or more of Embodiments 1 to 12.

Embodiment 14

The thermoplastic composition of Embodiment 13 further comprising apolycarbonate homopolymer, an additional poly(ester-carbonate), or acombination comprising at least one of the foregoing.

Embodiment 15

The poly(ester-carbonate) or the composition of any one or more ofEmbodiments 1 to 14, wherein a metalized sample of thepoly(ester-carbonate) or the composition has a defect onset temperaturethat is within 20 degrees Celcius preferably within 10 degrees Celciusof the heat deflection temperature of the poly(ester-carbonate) orcomposition measured flat on a 80×10×4 mm bar with a 64 mm span at 0.45MPa according to ISO 75/Bf.

Embodiment 16

The poly(ester-carbonate) or the composition of any one or more ofEmbodiments 1 to 14, wherein a metalized sample of thepoly(ester-carbonate) or the composition has a defect onset temperatureof 200 to 220° C.

Embodiment 17

The poly(ester-carbonate) or the composition of any one or more ofEmbodiments 1 to 16, wherein the composition at a given temperature hasa melt viscosity of less than 900 Pa·s at 644.5 sec⁻¹ and has a shift inmelt viscosity of less than 25% at the given temperature over 30 minunder a nitrogen atmosphere as measured in a small amplitude oscillatorytime sweep rheology at a fixed angular frequency of 10 radians/sec.

Embodiment 18

An article, wherein the article is a molded article, a thermoformedarticle, an extruded film, an extruded sheet, one or more layers of amulti-layer article, a substrate for a coated article, and a substratefor a metallized article made from the poly(ester-carbonate) orcomposition of any one or more of Embodiments 1 to 17.

Embodiment 19

A metallized article comprising the poly(ester-carbonate) or compositionof any one or more of Embodiments 1 to 17 wherein the defect onsettemperature of the metallized article is within 20 degrees Celciuspreferably within 10 degrees Celcius of the heat deflection temperatureof the poly(ester-carbonate) or the composition measured flat on a80×10×4 mm bar with a 64 mm span at 0.45 MPa according to ISO 75/Bf.

Embodiment 20

A metallized article, comprising a substrate comprising thepoly(ester-carbonate) or composition of any one of Embodiments 1-17; anda metal layer disposed on at least one side of the substrate.

Embodiment 21

The article of Embodiment 20, further comprising a protective layerdisposed on the metal layer.

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise. “Or” means “and/or.” Theendpoints of all ranges directed to the same component or property areinclusive and independently combinable.

Unless defined otherwise, technical and scientific terms used hereinhave the same meaning as is commonly understood by one of skill in theart to which this invention belongs. As used herein, a “combination” isinclusive of blends, mixtures, alloys, reaction products, and the like.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valency filled by a bond as indicated, or a hydrogen atom. A dash(“-”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group.

As used herein, the term “hydrocarbyl” and “hydrocarbon” refers broadlyto a substituent comprising carbon and hydrogen, optionally with 1 to 3heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, ora combination thereof; “alkyl” refers to a straight or branched chain,saturated monovalent hydrocarbon group; “alkylene” refers to a straightor branched chain, saturated, divalent hydrocarbon group; “alkylidene”refers to a straight or branched chain, saturated divalent hydrocarbongroup, with both valences on a single common carbon atom; “alkenyl”refers to a straight or branched chain monovalent hydrocarbon grouphaving at least two carbons joined by a carbon-carbon double bond;“cycloalkyl” refers to a non-aromatic monovalent monocyclic ormulticylic hydrocarbon group having at least three carbon atoms;“cycloalkylene” refers to a divalent radical formed by the removal oftwo hydrogen atoms from two different carbon atoms on one or more ringsof a cycloalkyl group; “aryl” refers to an aromatic monovalent groupcontaining only carbon in the aromatic ring or rings; “arylene” refersto an aromatic divalent group containing only carbon in the aromaticring or rings; “alkylaryl” refers to an aryl group that has beensubstituted with an alkyl group as defined above, with 4-methylphenylbeing an exemplary alkylaryl group; “arylalkyl” refers to an alkyl groupthat has been substituted with an aryl group as defined above, withbenzyl being an exemplary arylalkyl group; “acyl” refers to an alkylgroup as defined above with the indicated number of carbon atomsattached through a carbonyl carbon bridge (—C(═O)—); “alkoxy” refers toan alkyl group as defined above with the indicated number of carbonatoms attached through an oxygen bridge (—O—); and “aryloxy” refers toan aryl group as defined above with the indicated number of carbon atomsattached through an oxygen bridge (—O—).

Unless otherwise indicated, each of the foregoing groups can beunsubstituted or substituted, provided that the substitution does notsignificantly adversely affect synthesis, stability, or use of thecompound. The term “substituted” as used herein means that at least onehydrogen on the designated atom or group is replaced with another group,provided that the designated atom's normal valence is not exceeded. Whenthe substituent is oxo (i.e., ═O), then two hydrogens on the atom arereplaced. Combinations of substituents or variables are permissibleprovided that the substitutions do not significantly adversely affectsynthesis or use of the compound. Groups that can be present on asubstituted position include nitro (—NO₂), cyano (—CN), hydroxy (—OH),halogen, thiol (—SH), thiocyano (—SCN), C₂₋₆ alkanoyl (e.g., acyl(H₃CC(═O)—); carboxamido; C₁₋₆ or C₁₋₃ alkyl, cycloalkyl, alkenyl, andalkynyl (including groups having at least one unsaturated linkages andfrom 2 to 8, or 2 to 6 carbon atoms); C₁₋₆ or C₁₋₃ alkoxy; C₆₋₁₀ aryloxysuch as phenoxy; C₁₋₆ alkylthio; C₁₋₆ or C₁₋₃ alkylsulfinyl; C₁₋₆ orC₁₋₃ alkylsulfonyl; aminodi(C₁₋₆ or C₁₋₃)alkyl; C₆₋₁₂ aryl having atleast one aromatic rings (e.g., phenyl, biphenyl, naphthyl, or the like,each ring either substituted or unsubstituted aromatic); C₇₋₁₉ arylalkylhaving 1 to 3 separate or fused rings and from 6 to 18 ring carbonatoms; or arylalkoxy having 1 1 to 3 separate or fused rings and from 6to 18 ring carbon atoms.

All references cited herein are incorporated by reference in theirentirety. While typical embodiments have been set forth for the purposeof illustration, the foregoing descriptions should not be deemed to be alimitation on the scope herein. Accordingly, various modifications,adaptations, and alternatives can occur to one skilled in the artwithout departing from the spirit and scope herein.

1. A poly(carbonate-ester) copolymer comprising carbonate units of theformula

ester units of the formula

wherein: T is a C₂₋₂₀ alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀arylene; and R¹ and J are each independently a bisphenol A divalentgroup of the formula

or a phthalimidine divalent group of the formula

wherein R^(a) and R^(b) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy, each R³ is independently aC₁₋₆ alkyl, R⁴ is hydrogen, C₁₋₆ alkyl or phenyl optionally substitutedwith 1 to 5 C₁₋₆ alkyl groups, p, q, and j are each independently 0 to4, or a third divalent group of the formula

wherein R^(c) and R^(d) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy, each R⁶ is independently C₁₋₃alkyl or phenyl, X^(a) is a C₆₋₁₂ polycyclic aryl, C₃₋₁₈ mono- orpolycycloalkylene, C₃₋₁₈ mono- or polycycloalkylidene,-(Q¹)_(x)-G-(Q²)_(y)- group wherein Q¹ and Q² are each independently aC₁₋₃ alkylene, G is a C₃₋₁₀ cycloalkylene, x is 0 or 1, and y is 1, andm and n are each independently 0 to 4, provided that the at least onebisphenol A divalent group, at least one phthalimidine divalent group,and at least one third divalent group are present in thepoly(carbonate-ester) copolymer.
 2. The poly(carbonate-ester) copolymerof claim 1, wherein T is a C₆₋₂₀ divalent aromatic radical.
 3. Thepoly(carbonate-ester) copolymer of claim 1, wherein T is a divalentisophthaloyl radical, a divalent terephthaloyl radical, or a combinationthereof.
 4. The poly(carbonate-ester) copolymer of claim 1, wherein themolar ratio of the carbonate units relative to the ester units is 2:1 to1:2.
 5. The poly(carbonate-ester) copolymer of claim 1, wherein p, q,and j are zero, and R⁴ is hydrogen, methyl, or phenyl.
 6. Thepoly(carbonate-ester) copolymer of claim 1, wherein the third divalentgroup has the structural formula

wherein each R¹ is independently hydrogen or C₁₋₄ alkyl, each R² isindependently C₁₋₄ alkyl or hydrogen, and g is 0 to
 10. 7. Thepoly(carbonate-ester) copolymer of claim 6, wherein R¹ is methyl orhydrogen, R² is methyl or ethyl, and g is 0 to
 3. 8. Thepoly(carbonate-ester) copolymer of claim 1, wherein the third divalentgroup is derived from1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane.
 9. Thepoly(carbonate-ester) copolymer of any one or more of claim 1, whereinthe third divalent group has the structural formula

wherein R^(c) and R^(d) are each independently a C₁₋₁₂ alkyl, C₁₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy; and m and n are eachindependently 0 to
 4. 10. The poly(carbonate-ester) copolymer of claim1, wherein the phthalimidine divalent group is present in an amount of 5mol % to 30 mol % based on the sum of the moles of the bisphenol Adivalent group, the phthalimidine divalent group, and the third divalentgroup.
 11. The poly(carbonate-ester) copolymer of claim 1, wherein thirddivalent group is present in an amount of 2 mol % to 50 mol % based onthe sum of the moles of the bisphenol A divalent group, thephthalimidine divalent group, and the third divalent group.
 12. Thepoly(carbonate-ester) copolymer of claim 1, wherein the bisphenol Adivalent group is present in an amount of 45 mol % to 70 mol % based onthe sum of the moles of the bisphenol A divalent group, thephthalimidine divalent, and the third divalent group.
 13. Athermoplastic composition comprising a poly(carbonate-ester) copolymerof claim
 1. 14. The thermoplastic composition of claim 13 furthercomprising a polycarbonate homopolymer, an additionalpoly(ester-carbonate), or a combination comprising at least one of theforegoing.
 15. The poly(ester-carbonate) or the composition of claim 1,wherein a metalized sample of the poly(ester-carbonate) or thecomposition has a defect onset temperature that is within 10 degreesCelcius of the heat deflection temperature of the poly(ester-carbonate)or composition measured flat on a 80×10×4 mm bar with a 64 mm span at0.45 MPa according to ISO 75/Bf.
 16. The poly(ester-carbonate) or thecomposition of claim 1, wherein a metalized sample of thepoly(ester-carbonate) or the composition has a defect onset temperatureof 200 to 220° C.
 17. The poly(ester-carbonate) or the composition ofclaim 1, wherein the composition at a given temperature has a meltviscosity of less than 900 Pa·s at 644.5 sec⁻¹ and has a shift in meltviscosity of less than 25% at the given temperature over 30 min under anitrogen atmosphere as measured in a small amplitude oscillatory timesweep rheology at a fixed angular frequency of 10 radians/sec.
 18. Anarticle, wherein the article is a molded article, a thermoformedarticle, an extruded film, an extruded sheet, one or more layers of amulti-layer article, a substrate for a coated article, and a substratefor a metallized article made from the poly(ester-carbonate) orcomposition of claim
 1. 19. A metallized article comprising thepoly(ester-carbonate) or composition of claim 1 wherein the defect onsettemperature of the metallized article is within 10 degrees Celcius ofthe heat deflection temperature of the poly(ester-carbonate) or thecomposition measured in accordance with measured flat on a 80×10×4 mmbar with a 64 mm span at 0.45 MPa according to ISO 75/Bf.
 20. Ametallized article, comprising a substrate comprising thepoly(ester-carbonate) or composition of claim 1; and a metal layerdisposed on at least one side of the substrate.